M. Hanack, S. I. Vagin et al.
applicability for further chemical modification. Collected compounds 5
and 6 were purified by means of additional chromatography followed by
washing with ꢀ90% aqueous MeOH and drying. Yields: 130 mg (5.3%)
of 5 and 50 mg (4.4%) of 6.
(100) [M]+, 1246.9 (80) [MÀN2]+ (overlaps with [MÀ24]+); MALDI-
TOF (CH2Cl2): m/z calcd for [M+H]+: 1275.6; found: m/z (%): 1276.0
(100) [M+H]+, 1248.0 (80) [MÀN2]+ (overlaps with [MÀ24]+); elemen-
tal analysis calcd (%) for C80H82N12Zn1.5H2O (1277 + 27 gmolÀ1): C
73.69, H 6.57, N 12.89ꢀ; found: C 73.58, H 6.69, N 12.80.
Data for 5: 1H NMR (250 MHz, CDCl3 + ꢀ1% tBuNH2): d=0.90 (s,
Oxidation of 8 in THF: Pb(OAc)4 (95%, 13 mg, 28 mmol) was added to a
A
ꢀ75H; tBuNH2), 1.50, 1.51 (2s, 54H;
C
N
solution of 8 (30 mg, 23 mmol) in not absolutized THF (0.75 mL) with
good stirring at room temperature. Immediate evolution of gas was ob-
served and the reaction mixture was stirred at room temperature for ad-
ditional 15 min. Then, 4-tert-butyl catechol (a few milligrams) was added
and the solvent was evaporated by air-blowing. The residue was subjected
to column chromatography on silica, by using pure CH2Cl2 first, followed
by addition of small amounts THF (0.3–1%). Several fractions consisting
of mixtures of zinc porphyrazines were collected (see Results and Discus-
sion). The largest fraction, collected as the last by using pure CH2Cl2,
gave 4 mg of acceptably pure compound 12 {2,3,7,8,12,13-hexakis-(4-tert-
tBuNH2): d=31.59, 31.61 (2s, C
A
34.84 (3s, C(CH3)3), 47.4 (s, tBuNH2), 50.2 (s, CH3OH), 110.0 (brs, a-C),
C
124.92, 124.98 (2s, m-C), 125.17 (s, m’-C), 131.4, 131.6, 131.8 (3s, 3-C),
132.5 (s, o-, o’-C), 137.3 (br), 139.8, 140.5, 141.9, 142.3 (br) (5s, b-, g-, 2-
C), 150.0, 150.36, 150.43 (3s, 4-C), 155.2, 155.8, 157.9, 158.9 ppm (4s, d-,
1-C); FTIR (KBr): n˜ =3080 (vw), 3037 (vw), 2962 (vs), 2904 (m), 2868
(m), 1625 (w), 1610 (w), 1520 (w), 1474 (m), 1450 (w), 1383 (w), 1364
(m), 1327 (vw), 1269 (m), 1199 (w), 1159 (w), 1132 (w), 1103 (m), 1018
(vw), 993 (m), 979 (s), 893 (w), 882 (w), 839 (m), 808 (vw), 797 (vw), 759
(w), 745 (w), 667 (vw), 646 (vw) 629 (vw), 685 (vw), 567 (w), 534 cmÀ1
butylphenyl)(2-(4-acetoxybutyloxy)benzo[5,6-q])porphyrazinatozinc}
E
after washing with MeOH and drying (13% yield). 1H NMR (250 MHz,
CDCl3 + ꢀ1% tBuNH2): d=1.02, 1.09 (2s, tBuNH2), 1.487, 1.494, 1.524
(3s, 54H;
C(CH3)3), 1.96–2.14 (m, 4H; 2-, 3-H), 2.08 (s, 3H;
A
(vw); UV/Vis (CH2Cl2/1% THF): lmax(log(e))=364 (4.90), 580 (4.28),
G
3
3
OC(O)CH3), 4.25 (t, Jꢀ6.3 Hz, 2H; 4-H), 4.45 (t, Jꢀ6.1 Hz, 2H; 1-H),
629 (4.83), 680 nm (4.96); MS MALDI-TOF (CH2Cl2): m/z calcd for
[M+H]+: 1260.6; found: m/z (%): 1261.0 (100) [M+H]+; elemental anal-
3
4
7.55–7.60 (m, 8H; m-H), 7.63 (dd, Jꢀ8.2 Hz, Jꢀ2.3 Hz, 1H; b-H), 7.70
(d, 3Jꢀ8.4 Hz, 4H; m’-H), 8.30–8.40 (m, 12H; o-, o’-H), 8.69 (d, 4J
ꢀ2.2 Hz, 1H; a-H), 9.11 ppm (d, 3Jꢀ8.3 Hz, 1H; g-H) (see Supporting
Information); 13C-dept NMR (62.9 MHz, CDCl3 + ꢀ1% tBuNH2): d=
ysis calcd (%) for C80H81N11Zn0.5CH3OH (1262
75.66, H 6.55, N 12.06; found: C 75.69, H 6.67, N 11.87.
+
16 gmolÀ1): C
Data for 6: 1H NMR (250 MHz, [D8]THF): d=1.61, 1.63 (2s, 36H; C-
21.4 (s, OC(O)CH3), 25.9, 26.5 (2s, 2-, 3-C), 32.00, 32.03 (2s, C(CH3)3),
U
A
32.8 (s, tBuNH2), 64.5 (s, 4-C), 68.6 (s, 1-C), 107.7, 118.6, 124.8 (3s, a-, b-,
g-C), 125.37, 125.4, 125.5, 125.6 (4s, m-, m’-C), 132.96, 133.02 ppm (2s, o-,
o’-C); UV/Vis (CH2Cl2): lmax(rel. int.)=368 (0.957), 581 sh. (0.237), 630
(0.918), 671 nm (1.00). MALDI-TOF (CH2Cl2): m/z calcd for [M+H]+
1349.7; found: m/z (%): 1349.9 (100) [M+H]+; elemental analysis calcd
ꢀ8.0 Hz, 8H; o’-, o-H), 8.84, 9.25 (2brs, 4H; a, a’-H), 15.01 ppm (very
brs, <2H; NH) (see Supporting Information); 13C NMR (250 MHz,
[D8]THF): d=32.1, 32.2 (2s, C
N
N
m-, m’-C), 132.8, 133.3 (2s, 3-, 3’-C), 133.54, 133.59 (2s, o-, o’-C), 138.7,
141.0 (br) (2s, 2-, 2’-C), 150.50, 150.54 (2s, 4-, 4’-C), 152.6, 154.7 (br),
155.8 (br), 158.9 ppm (br) (4s, 1-, 1’-, d-, d’-C); signals of other carbon
atoms, close to the triazole moieties of 6, were not observed because of
the tautomeric conversions in triazole rings; FTIR (KBr): n˜ =2962 (vs),
2905 (s), 2867 (m), 1625 (m), 1525 (w), 1481 (m), 1449 (m), 1370 (s), 1339
(vw), 1269 (m), 1200 (m), 1188 (m), 1153 (w), 1138 (m), 1104 (m), 1055
(vw), 1018 (vw), 987 (vs), 890 (m), 869 (w), 840 (m), 802 (w), 773 (vw),
755 (m), 739 (w), 678 (vw), 657 (w), 626 (w), 565 (m), 524 cmÀ1 (w); UV/
(%) for C86H86N8Zn2C4H9NH2 (from NMR solvent) (1297
+
146 gmolÀ1): C 75.40, H 7.67, N 9.35; found: C 75.63, H 7.46, N 9.89.
Oxidation of 8 in benzene: Compound 8 (15 mg, 11.5 mmol) was dissolved
in benzene (1.4 mL), preliminarily dried over sodium. Pb(OAc)4 (6.5 mg,
AHCTREUNG
14 mmol) was added with good stirring to this solution at room tempera-
ture. Immediate evolution of gas could be observed during few seconds.
After 1 h, 4-tert-butyl catechol (a few milligrams) was added, and the re-
action mixture was transferred to a chromatographic column. Elution
with CH2Cl2 allowed the collection of two well-separable fractions. First
fraction gave 6 mg (ꢀ40%) of compound 14, the second fraction con-
tained 2 mg (ꢀ14%) 11. Addition of THF to the eluent allowed the elu-
tion nearly all colored material as a third fraction, consisting mainly of
deaminated starting material, namely compound 5.
Vis (CH2Cl2/1% THF): lmax(log(e)=363 (4.94), 604 (4.55), 670 nm (5.22);
T
MS MALDI-TOF (CH2Cl2): m/z calcd for [M+H]+ 1087.4; found: m/z
(%): 1087.8 (100) [M+H]+; elemental analysis calcd (%) for
C64H58N14ZnCH3OH (1089 + 32 gmolÀ1): C 69.66, H 5.58, N 17.50;
found: C 69.83, H 5.58, N 17.04.
2,3,7,8,12,13-Hexakis-(4-tert-butylphenyl)(1-amino-1,2,3-benzotriazole-
1
Data for 14: H NMR (250 MHz, [D8]THF): d=1.50, 1.51, 1.59 (3s, 54H;
A
our earlier described procedure,[2] by using 5 (55 mg, 43 mmol), 2,4-dini-
tro-O-aminophenol (DNAP) (200 mg, 1.48 mmol), KOH (1.14 g,
20.4 mmol), THF (6 mL) and H2O (2 mL). In the course of purification,
65–70% aqueous acetonitrile was used for washing 8 on the filter, THF/
CH2Cl2 was applied to wash it down from the filter, followed by evapora-
tion to dryness. Aqueous methanol (80–85%) was used for decantation.
Yield 53 mg (95%); 1H NMR (250 MHz, [D8]THF): d=1.52, 1.54, 1.58,
tBu), 5.49 (m, 2H; 5-H), 7.12 (m, 4H; 6-H), 7.54–7.62 (m, 8H; m-H),
3
7.78 (d, Jꢀ8.1 Hz, 4H; m’-H), 8.29–8.42 (m, 12H; o-, o’-H), 8.96 ppm (s,
2H; a-H); 13C-dept NMR (62.9 MHz, [D8]THF): d=31.43, 31.47 (2s, C-
(CH3)3), 50.5 (s, 5-C), 116.8 (s, a-C), 125.06, 125.17 (2s, m-, m’-C), 132.94,
132.99 (2s, o-, o’-C), 140.0 ppm (s, 6-C); UV/Vis (CH2Cl2): lmax(rel.
int.)=364 (1.00), 581 sh. (0.252), 630 (0.938), 665 nm (0.983); MS
MALDI-TOF (THF): m/z calcd for [M]+: 1294.6; found: m/z (%): 1294.8
(100) [M]+; elemental analysis calcd (%) for C86H86N8ZnH2O (1297 +
18 gmolÀ1): C 78.55, H 6.74, N 8.52; found: C 78.27, H 6.74, N 9.22.
1.60 (4s, 54H; C(CH3)3), 7.00 (s, 2H; NH2), 7.55–7.63 (m, 8H; m-H),
G
7.73, 7.78 (2d, 3J= ꢀ8.4 Hz, 4H; m’-H), 8.26–8.40 (m, 12H; o-, o’-H),
1
9.23 (s, 1H; a-H), 9.56 ppm (s, 1H; a’-H); 13C NMR (62.9 MHz,
Data for 11: H NMR (250 MHz, CDCl3 + ꢀ1% tBuNH2): d=1.05, 1.15
(2s, tBuNH2), 1.48, 1.52 (2s, 54H; C(CH3)3), 2.52 (s, 3H; OC(O)CH3),
R
[D8]THF): d=32.03, 32.06, 32.11 (3s, C
A
7.54–7.60 (m, 8H; m-H), 7.70 (d, 3Jꢀ8.0 Hz, 4H; m’-H), 7.81 (dd, 3J
ꢀ8.0 Hz, 4Jꢀ2.0 Hz, 1H; b-H), 8.27–8.39 (m, 12H; o-, o’-H), 8.91 (d, 4J
ꢀ2.0 Hz, 1H; a-H), 9.24 ppm (d, 3Jꢀ8.0 Hz, 1H; g-H); 13C-dept NMR
(62.9 MHz, CDCl3 + ꢀ1% tBuNH2): d=21.8 (s, OC(O)CH3), 32.0 (s, C-
(4s, C(CH3)3), 105.2 (s, a’-C), 115.1 (s, a-C), 125.60, 125.63, 125.68, 125.82
ACHTREUNG
(4s, m-, m’-C), 132.52, 132.60, 132.85, 132.96, 132.98 (5s, 3-C), 133.51,
133.57 (2s, o-, o’-C), 135.5, 137.1, 140.0, 140.7, 141.0, 141.3, 141.5, 142.6,
142.8, 147.1 (10s, b-, g-, 2-C), 150.7, 151.0, 151.1, 151.3 (4s, 4-C), 155.5,
155.7, 155.9, 156.5, 157.4, 158.1, 159.0, 159.5 ppm (8s, d-, 1-C); FTIR
(KBr): n˜ =3080 (vw), 3036 (vw), 2961 (vs), 2904 (s), 2867 (m), 1633 (m),
1612 (m), 1521 (w), 1475 (s), 1450 (w), 1364 (s), 1328 (vw), 1269 (m),
1199 (w), 1161 (w), 1131 (w), 1103 (s), 1017 (vw), 993 (s), 978 (vs), 893
(w), 881 (w), 838 (s), 810 (vw), 799 (vw), 773 (vw), 759 (m), 746 (m), 671
(vw), 585 (vw), 567 cmÀ1 (m); UV/Vis (CH2Cl2/1% THF): lmax(rel. int.)=
365 (0.891), 377 (0.851), 581 (0.229), 630 (0.776), 681 nm (1.00); MS
MALDI-TOF (THF): m/z calcd for [M]+: 1274.6; found: m/z (%): 1274.9
A
125.62, 125.66 (3s, m-, m’-C), 132.90, 132.98, 133.01 ppm (3s, o-, o’-C);
MS MALDI-TOF (THF): m/z calcd for [M]+: 1276.6; found: m/z (%):
1276.8 (100) [M]+.
Oxidation of 1-aminobenzotriazole (15) in benzene: Compound 15
(72 mg, 0.54 mmol) was dissolved in dry benzene (70 mL) and Pb(OAc)4
T
(260 mg, 0.56 mmol) was added in one portion with stirring. After ꢀ1 h
the solution was filtered and the solvent was removed under reduced
990
ꢁ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2007, 13, 985 – 991